Naturally-occurring angular tricyclic benzofuran/isobenzofuran derivatives of fungal origin and related compounds, in which two heterocyclic rings are fused to a central benzenoid moiety, are covered. Emphasis is placed on the structure of the compounds, together with their relevant biological activities, source microorganisms, country or region of origin and environmental conditions. In addition, proposed biosynthetic pathways, as well as the total syntheses of some of the compounds, including those that lead to structural revision or to correct stereochemical assignments, and related synthetic efforts, are discussed in detail.